Skip to main content
SpringerLink
Log in

Role of ligands in controlling the regioselectivity in ruthenium-catalysed addition of carboxylic acids to terminal alkynes: A DFT study

  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Density functional studies are performed to understand the role of chelating bi-phosphine ligands [(Ph 2P(CH 2) m PPh 2); m = 1–4] in modulating the regio-selectivity of benzoic acid addition to 1-hexyne, in presence of ruthenium(II) catalyst [(Ph 2P(CH 2)mPPh 2)Ru(methallyl) 2]. The Markovnikov addition to 1-hexyne is observed when catalyst 1 a [(Ph 2P(CH 2)PPh 2)Ru(methallyl) 2] is employed, whereas a reverse regio-selectivity is witnessed in presence of 1 d [(Ph 2P(CH 2)4PPh 2)Ru(methallyl) 2]. Anti-Markovnikov addition occurs via the neutral vinylidene intermediates (5 a / d ) formed after 1,2-hydrogen shift in hexyne coordinated ruthenium(II) complexes 3 a / d . The energy profile shows clear preference for Markovnikov addition by 15.0 kcal/mol (\({\Delta } G_{\mathrm {L}}^{S})\) in case of catalyst system 1 a . In contrast, anti-Markovnikov pathway following neutral vinylidenes are more favourable by 9.1 kcal/mol (\({\Delta } G_{\mathrm {L}}^{S})\) for catalyst system 1 d . The Z-enol ester formation is more predominant in the anti-Markovnikov pathway since the activation barrier for this step requires less energy (5.9 kcal/mol, \({\Delta } G_{\mathrm {L}}^{S})\) than the one furnishing the E-product. The calculated results are in good agreement with the reported experimental findings.

Preliminary DFT studies are performed to explore the mechanistic pathway of the benzoic acid addition to 1-hexyne in presence of Ru(II) catalyst. Our calculations emphasized on the understanding of the regio-selectivity controlled by the chelating bi-phosphine ligand present in catalysts. Markovnikov product formation is the lower energy pathway in case of least spacer group (CH2) whereas it is anti-Markovnikov product for the highest spacer group, {(CH2)4} in bi-phosphine ligands.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Scheme 4
Figure 1
Scheme 5
Figure 2
Figure 3
Scheme 6
Scheme 7
Scheme 8
Figure 4
Figure 5

Similar content being viewed by others

References

  1. (a) Rozen S and Lerman O 1979 J. Am. Chem. Soc. 101 2782; (b) Wexler A, Balchunis R J and Swenton J S 1975 J. Chem. Soc., Chem. Commun. 15 601; (c) House H O 1972 Modern synthetic reactions, 2 nd edn Menlo Park, CA: W A Benjamin 313. (d) Tsuji J, Minami I and Shimizu I 1983 Tetrahedron Lett. 24 4713; (e) Schmitt G Warwel S, Homminga E and Meltzow W 1972 Justus Liebigs Ann. Chem. 763 75

  2. (a) Monthéard J P, Camps M, Seytre G, Guillet J and Dubois J C 1978 Angew. Makromol. Chem. 72 45; (b) Seidel A, Jägers E and Bylsma F 1993 Eur. Pat. 0574 725 A1

  3. Rotem M and Shvo Y 1983 Organometallics 2 1689

  4. (a) Mitsudo T, Hori Y and Watanabe Y 1985 J. Org. Chem. 50 1566 (b) Mitsudo T, Hori Y, Yamakawa Y and Watanabe Y 1987 J. Org. Chem. 52 2230

  5. (a) Doucet H, Hofer J, Bruneau C and Dixneuf P H 1993 J. Chem. Soc., Chem. Commun. 10 850 (b) Doucet H, Martin-Vanca B, Bruneau C and Dixneuf P H 1995 J. Org. Chem. 60 7247 (c) Doucet P, Derrien N, Kabouche Z, Bruneau C and Dixneuf P H 1997 J. Organomet. Chem. 551 151 (d) Bruneau C and Dixneuf P H 1999 Acc. Chem. Res. 32 311 and references therein

  6. Bruneau C, Neveux-Duflos M and Dixneuf P H 1999 Green Chem. 1 183

  7. Goossen L J, Paetzold J and Koley D 2003 Chem. Commun. 6 706

  8. (a) Bruneau C and Dixneuf P H 2008 Angew. Chem. Int. Ed. 47 8492 (b) Rigaut S, Touchard D and Dixneuf P H 2004 Coord. Chem. Rev. 248 1585

  9. Gaussian 09, Revision C.01, Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A, Nakatsuji H, Caricato M, Li X, Hratchian H P, Izmaylov A F, Bloino J, Zheng G, Sonnenberg J L, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven, T, Montgomery Jr J A, Peralta J E, Ogliaro F, Bearpark M, Heyd J J, Brothers E, Kudin K N, Staroverov V N, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant J C, Iyengar S S, Tomasi J, Cossi M, Rega N, Millam J M, Klene M, Knox J E, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Martin R L, Morokuma K, Zakrzewski V G, Voth G A, Salvador P, Dannenberg J J, Dapprich, S, Daniels A D, Farkas Ö, Foresman J B, Ortiz J V, Cioslowski J and Fox D J Gaussian, Inc., Wallingford CT, 2010

  10. (a) Maseras F and Morokuma K 1995 J. Comput. Chem. 16 1170 (b) Vrevenand T and Morokuma K 2000 J. Comput.Chem. 21 1419

  11. (a) Hay P J and Wadt W 1985 J. Chem. Phys. 82 270 (b) Hay P J, and Wadt W 1985 J. Chem. Phys. 82 284 (c) Hay P J and Wadt W 1985 J. Chem. Phys. 82 299

  12. Hehre W J, Radom L, Schleyer P v R and Pople J A 1986 Ab initio molecular orbital theory (New York: Wiley)

  13. Helgren T A and Lipscomb W N 1977 Chem. Phys. Lett. 49 225

  14. Marenich A V, Cramer C J and Truhlar D 2009 J. Phys. Chem. B 113 6378

  15. Reed A E, Curtiss L A and Weinhold F 1998 Chem. Rev. 88 899

  16. (a) Oliván M, Eisenstein O and Caulton K G 1997 Organometallics 16 2227 (b) Oliván M, Clot E, Eisenstein O and Caulton K G 1998 Organometallics 17 3091

  17. Kostic N M and Fenske R F 1982 Organometallics 1 974

  18. Bruneau C and Dixneuf P H 2006 Angew. Chem. 118 2232; Angew. Chem. Int. Ed. 45 2176

  19. Varela-Fernández A, González-Rodríguez C, Varela J A, Castedo L and Saá C 2009 Org. Lett. 11 5350

  20. Wakatsuki Y, Koga N, Yamazaki H and Morokuma K 1994 J. Am. Chem. Soc. 116 8105

  21. Tokunaga M, Suzuki T, Koga N, Fukushima T, Horiuchi A and Wakatsuki Y 2001 J. Am. Chem. Soc. 123 11917

  22. (a) Höhn A, Otto H, Dziallas M and Werner H 1987 J. Chem. Soc., Chem. Commun. 852 (b) Alonso F J G, Höhn A, Wolf J, Otto H and Werner H 1985 Angew. Chem. Int. Ed. 24 406

  23. Cadierno V, Gamasa M P and Gimeno J 1999 Organometallics 18 2821

  24. Silvestre J and Hoffmann R 1985 Helv. Chim. Acta. 68 1461

  25. Arndt M, Salih K S M, Fromm A, Goossen L J, Menges F and Schatteburg G N 2011 J. Am. Chem. Soc. 133 7428

  26. (a) Gooßen L J, Koley D, Hermann H L and Thiel W 2004 Chem. Commun. 19 2141 (b) Goossen L J, Koley D, Hermann H L and Thiel W 2005 J. Am. Chem. Soc. 127, 11102

  27. Consiglio G, Morandini F, Ciani G F and Sironi A 1986 Organometallics 5 1976

Download references

Acknowledgement

The authors are thankful to IISER-Kolkata for providing computational facility. BM and TM are thankful to CSIR for their respective SRF and JRF fellowships. KD and SB gratefully acknowledge INSPIRE, DST. DK acknowledges IISER-Kolkata for start-up grant and SERB for DST fast track fellowship (SR/FT/SC-72/2011).

Author information

Authors and Affiliations

  1. Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur, 741 246, India

    BHOLANATH MAITY, TOTAN MONDAL, KAUSTAV DEY, SANKARSAN BISWAS & DEBASIS KOLEY

Authors
  1. BHOLANATH MAITY
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. TOTAN MONDAL
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. KAUSTAV DEY
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. SANKARSAN BISWAS
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. DEBASIS KOLEY
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to DEBASIS KOLEY.

Additional information

Supplementary Information

Steric effect in ligand exchange step (1 x → 2 x ) and related optimized geometries are given in scheme S1 and figure S1. Figure S2 represents the oxidative addition in 3 d intermediate. KS-LUMO of 5 d and nucleophilic approach of that intermediate are shown in figure S2. Absolute total energy (in Hartrees) and Cartesian coordinates of all intermediates and transition states are shown in tables S1 and S2, respectively. For details see www.ias.ac.in/chemsci website.

Electronic supplementary material

Below is the link to the electronic supplementary material.

(PDF 609 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

MAITY, B., MONDAL, T., DEY, K. et al. Role of ligands in controlling the regioselectivity in ruthenium-catalysed addition of carboxylic acids to terminal alkynes: A DFT study. J Chem Sci 127, 281–293 (2015). https://doi.org/10.1007/s12039-015-0775-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-015-0775-4

Keywords

Search

Navigation